U.S. patent application number 12/213953 was filed with the patent office on 2009-01-29 for ethynylphenylbiadamantane derivatives.
Invention is credited to Shigehiro Maeda, Yasuhito Nakai.
Application Number | 20090030248 12/213953 |
Document ID | / |
Family ID | 39941513 |
Filed Date | 2009-01-29 |
United States Patent
Application |
20090030248 |
Kind Code |
A1 |
Nakai; Yasuhito ; et
al. |
January 29, 2009 |
Ethynylphenylbiadamantane derivatives
Abstract
Disclosed is a halophenylbiadamantane derivative of following
Formula (1): ##STR00001## wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, and R.sup.6 each independently represent, for
example, a hydrogen atom or a halo-substituted or unsubstituted
alkyl or cycloalkyl group having about six or less carbon atom(s),
provided that at least one of R.sup.1 to R.sup.6 represents a
substituent represented by following Formula (2): ##STR00002##
wherein X represents a halogen atom; and "n" denotes a natural
number of 1 to 5, wherein when only one of R.sup.1 to R.sup.6 is a
substituent of Formula (2), then at least one of R.sup.1 to R.sup.6
is a halo-substituted or unsubstituted alkyl or cycloalkyl group
having about six or less carbon atom(s) or "n" is a natural number
of 2 or more. The halophenylbiadamantane derivative is usable as an
intermediate material for a wide variety of biadamantane
derivatives.
Inventors: |
Nakai; Yasuhito;
(Himeji-shi, JP) ; Maeda; Shigehiro; (Tokyo,
JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Family ID: |
39941513 |
Appl. No.: |
12/213953 |
Filed: |
June 26, 2008 |
Current U.S.
Class: |
570/183 |
Current CPC
Class: |
C07F 7/0805 20130101;
C07C 25/22 20130101; C07C 13/615 20130101; C07C 2603/74
20170501 |
Class at
Publication: |
570/183 |
International
Class: |
C07C 25/22 20060101
C07C025/22 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 5, 2007 |
JP |
2007-176956 |
Claims
1. A halophenylbiadamantane derivative represented by following
Formula (1): ##STR00022## wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, and R.sup.6 are the same as or different from one
another and each represent a hydrogen atom, a halo-substituted or
unsubstituted alkyl or cycloalkyl group having about six or less
carbon atom(s), a substituted or unsubstituted phenyl group, a
carboxyl group, a substituted or unsubstituted carbamoyl group, a
substituted oxycarbonyl group, a substituted or unsubstituted amino
group, a halogen atom, or a hydroxyl group, with the proviso that
at least one of R.sup.1 to R.sup.6 represents a substituent
represented by following Formula (2): ##STR00023## wherein X
represents a halogen atom; and "n" denotes a natural number of 1 to
5, wherein when two or more of R.sup.1 to R.sup.6 represent
substituents of Formula (2), these substituents may be the same as
or different from one another, wherein the benzene ring in Formula
(2) may further have an alkyl or cycloalkyl group having about six
or less carbon atoms in addition to the halogen atom(s), and
wherein when only one of R.sup.1 to R.sup.6 is a substituent of
Formula (2), then at least one of R.sup.1 to R.sup.6 is a
halo-substituted or unsubstituted alkyl or cycloalkyl group having
about six or less carbon atom(s) or "n" is a natural number of 2 or
more.
2. An ethynylphenylbiadamantane derivative represented by following
Formula (3): ##STR00024## wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, and R.sup.6 are the same as or different from one
another and each represent a hydrogen atom, a halo-substituted or
unsubstituted alkyl or cycloalkyl group having about six or less
carbon atom(s), a substituted or unsubstituted phenyl group, a
carboxyl group, a substituted or unsubstituted carbamoyl group, a
substituted oxycarbonyl group, a substituted or unsubstituted amino
group, a halogen atom, or a hydroxyl group, with the proviso that
at least one of R.sup.1 to R.sup.6 represents a substituent
represented by following Formula (4): ##STR00025## wherein Y
represents a hydrogen atom, an alkyl group having about one to
about six carbon atoms, a phenyl group, or a tri-substituted silyl
group; and "n" denotes a natural number of 1 to 5, wherein when two
or more of R.sup.1 to R.sup.6 represent substituents of Formula
(4), these substituents may be the same as or different from one
another, and wherein when "n" is 1 in all the substituent(s) of
Formula (4) as R.sup.1 to R.sup.6, then at least one of R.sup.1 to
R.sup.6 is a halo-substituted or unsubstituted alkyl or cycloalkyl
group having about six or less carbon atom(s).
3. A process for the preparation of ethynylphenylbiadamantane
derivatives, the process comprising the step of reacting a
halophenyladamantane derivative with a terminal alkyne to give an
ethynylphenylbiadamantane derivative, the halophenyladamantane
derivative represented by following Formula (1a): ##STR00026##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6
are the same as or different from one another and each represent a
hydrogen atom, a halo-substituted or unsubstituted alkyl or
cycloalkyl group having about six or less carbon atom(s), a
substituted or unsubstituted phenyl group, a carboxyl group, a
substituted or unsubstituted carbamoyl group, a substituted
oxycarbonyl group, a substituted or unsubstituted amino group, a
halogen atom, or a hydroxyl group, with the proviso that at least
one of R.sup.1 to R.sup.6 represents a substituent represented by
following Formula (2): ##STR00027## wherein X represents a halogen
atom; and "n" denotes a natural number of 1 to 5, wherein, when two
or more of R.sup.1 to R.sup.6 represent substituents of Formula
(2), these substituents may be the same as or different from one
another, wherein the benzene ring in Formula (2) may further have
an alkyl or cycloalkyl group having about six or less carbon atoms
in addition to the halogen atom(s), and wherein when "n" is 1 in
all the substituent(s) of Formula (2) as R.sup.1 to R.sup.6, then
at least one of R.sup.1 to R.sup.6 is a halo-substituted or
unsubstituted alkyl or cycloalkyl group having about six or less
carbon atom(s), the terminal alykyne represented by following
Formula (5): R'--C.ident.C--Y (5) wherein Y represents a hydrogen
atom, an alkyl group having about one to about six carbon atoms, a
phenyl group, or a tri-substituted silyl group; and R' represents a
hydrogen atom or a metal atom, and the ethynylphenylbiadamantane
derivative represented by following Formula (3): ##STR00028##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6
are the same as or different from one another and each represent a
hydrogen atom, a halo-substituted or unsubstituted alkyl or
cycloalkyl group having about six or less carbon atom(s), a
substituted or unsubstituted phenyl group, a carboxyl group, a
substituted or unsubstituted carbamoyl group, a substituted
oxycarbonyl group, a substituted or unsubstituted amino group, a
halogen atom, or a hydroxyl group, with the proviso that at least
one of R.sup.1 to R.sup.6 represents a substituent represented by
following Formula (4): ##STR00029## wherein Y represents a hydrogen
atom, an alkyl group having about one to about six carbon atoms, a
phenyl group, or a tri-substituted silyl group; and "n" denotes a
natural number of 1 to 5, wherein when two or more of R.sup.1 to
R.sup.6 represent substituents of Formula (4), these substituents
may be the same as or different from one another, wherein when "n"
is 1 in all the substituent(s) of Formula (4) as R.sup.1 to
R.sup.6, then at least one of R.sup.1 to R.sup.6 is a
halo-substituted or unsubstituted alkyl or cycloalkyl group having
about six or less carbon atom(s).
4. A process for the preparation of ethynylphenylbiadamantane
derivatives, the process comprising the step of reacting an
ethynylphenylbiadamantane derivative (3a) with an alcohol compound
to give a ethynylphenylbiadamantane derivative (3b), the
ethynylphenylbiadamantane derivative (3a) represented by following
Formula (3a): ##STR00030## wherein R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, and R.sup.6 are the same as or different from one
another and each represent a hydrogen atom, a halo-substituted or
unsubstituted alkyl or cycloalkyl group having about six or less
carbon atom(s), a substituted or unsubstituted phenyl group, a
carboxyl group, a substituted or unsubstituted carbamoyl group, a
substituted oxycarbonyl group, a substituted or unsubstituted amino
group, a halogen atom, or a hydroxyl group, with the proviso that
at least one of R.sup.1 to R.sup.6 represents a substituent
represented by following Formula (4a): ##STR00031## wherein Y
represents a tri-substituted silyl group; and "n" denotes a natural
number of 1 to 5, wherein when two or more of R.sup.1 to R.sup.6
represent substituents of Formula (4a), these substituents may be
the same as or different from one another, wherein when "n" is 1 in
all the substituent(s) of Formula (4a) as R.sup.1 to R.sup.6, then
at least one of R.sup.1 to R.sup.6 is a halo-substituted or
unsubstituted alkyl or cycloalkyl group having about six or less
carbon atom(s) the ethynylphenylbiadamantane derivative (3b)
represented by following Formula (3b): ##STR00032## wherein
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 are the
same as or different from one another and each represent a hydrogen
atom, a halo-substituted or unsubstituted alkyl or cycloalkyl group
having about six or less carbon atom(s), a substituted or
unsubstituted phenyl group, a carboxyl group, a substituted or
unsubstituted carbamoyl group, a substituted oxycarbonyl group, a
substituted or unsubstituted amino group, a halogen atom, or a
hydroxyl group, with the proviso that at least one of R.sup.1 to
R.sup.6 represents a substituent represented by following Formula
(4b): ##STR00033## wherein "n" denotes a natural number of 1 to 5,
wherein when two or more of R.sup.1 to R.sup.6 represent
substituents of Formula (4b), these substituents may be the same as
or different from one another, wherein when "n" is 1 in all the
substituents(s) represented by Formula (4b) as R.sup.1 to R.sup.6,
then at least one of R.sup.1 to R.sup.6 is a halo-substituted or
unsubstituted alkyl or cycloalkyl group having about six or less
carbon atom(s).
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to novel
ethynylphenylbiadamantane derivatives that can be used typically as
materials for interlayer dielectric films of multilayer circuit
boards, materials for flexible printed circuit boards, and
materials for aerospace use. It also relates to novel
halophenylbiadamantane derivatives that can be used as starting
materials for a variety of adamantane derivatives, and processes
for the preparation of the ethynylphenylbiadamantane
derivatives.
[0003] 2. Description of the Related Art
[0004] Adamantane derivatives have stable carbon skeleton
structures, thereby have satisfactory properties such as thermal
stability, water resistance, optical properties, optical
transparency, low dielectric constant, and stiffness (rigidity),
and have been used as starting materials to give functional
materials, such as high-functional polymers, which excel typically
in thermal properties, mechanical properties, electrical
properties, and/or optical properties. Among such adamantane
derivatives, biadamantane derivatives each having two adamantane
skeletons bonded to each other further excel typically in thermal
properties as compared to adamantane and diadamantane derivatives
and are expected to be applied as starting materials to give
high-functional materials such as materials for electronic
components and optical components.
[0005] Additionally, there have been known techniques of forming a
polymer network to improve mechanical strength, by incorporating a
crosslinkable functional group into a monomer component or directly
into a polymer; and there have been proposed the application of an
adamantane derivative (Japanese Unexamined Patent Application
Publication (JP-A) No. 2003-292878), a diadamantane derivative
(JP-A No. 2006-257212), and a biadamantane derivative (JP-A No.
2005-516382) each having an ethynyl group, to give semiconductor
devices, such as porous dielectric films, which excel in dielectric
constant, mechanical strength, and thermal stability.
[0006] In this connection, the solubility of monomers in organic
solvents is an important factor upon preparation of polymers
containing adamantane skeletons. It is therefore desirable to
provide ethynyl-containing biadamantane derivatives that excel in
dielectric constant, mechanical strength, and thermal stability,
have higher solubility in organic solvents, and are advantageous in
production and processing.
[0007] On the other hand, halophenylbiadamantane derivatives can be
widely utilized as intermediate materials and are very useful,
because their halogen atom can be converted into a variety of
substituents such as carbonyl group, an alkyl group, phenyl group,
an alkenyl group, or alkynyl group (e.g., ethynyl group). However,
there has been disclosed no halophenylbiadamantane derivative but
3-(4-bromophenyl)-1,1'-biadamantane as a material for
1-(4-vinylphenyl)adamantane (JP-A No. 2006-96988) alone.
SUMMARY OF THE INVENTION
[0008] Accordingly, an object of the present invention is to
provide a novel ethynylphenylbiadamantane derivative that is useful
as a functional material excellent typically in electrical
properties, thermal properties, mechanical properties, and/or
physical properties.
[0009] Another object of the present invention is to provide a
novel halophenylbiadamantane derivative that is an intermediate
material for the ethynylphenylbiadamantane derivative and is widely
usable as an intermediate material for a variety of adamantane
derivatives.
[0010] Yet another object of the present invention is to provide a
process for the preparation of the ethynylphenylbiadamantane
derivative from the halophenylbiadamantane derivative.
[0011] After intensive investigations to achieve the above objects,
the present inventors found a novel ethynylphenylbiadamantane
derivative that has higher crosslinkability and higher solubility
in solvents than the known ethynylphenylbiadamantane derivative
having a monoethynylphenyl group.
[0012] They also found a novel halophenylbiadamantane derivative
that is an intermediate material for the ethynylphenylbiadamantane
derivative and, in addition, is usable as an intermediate material
for a wide variety of biadamantane derivatives.
[0013] They further found a process for efficiently preparing the
ethynylphenylbiadamantane derivative from the
halophenylbiadamantane derivative. Additionally, they also found a
process for deprotecting (removing a protecting group of) the
ethynylphenylbiadamantane derivative. The present invention has
been made based on these findings.
[0014] Specifically, according to an embodiment of the present
invention, there is provided a halophenylbiadamantane derivative
which is represented by following Formula (1):
##STR00003##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6
are the same as or different from one another and each represent a
hydrogen atom, a halo-substituted or unsubstituted alkyl or
cycloalkyl group having about six or less carbon atom(s), a
substituted or unsubstituted phenyl group, a carboxyl group, a
substituted or unsubstituted carbamoyl group, a substituted
oxycarbonyl group, a substituted or unsubstituted amino group, a
halogen atom, or a hydroxyl group, with the proviso that at least
one of R.sup.1 to R.sup.6 represents a substituent represented by
following Formula (2):
##STR00004##
wherein X represents a halogen atom; and "n" denotes a natural
number of 1 to 5, wherein when two or more of R.sup.1 to R.sup.6
represent substituents of Formula (2), these substituents may be
the same as or different from one another, wherein the benzene ring
in Formula (2) may further have an alkyl or cycloalkyl group having
about six or less carbon atoms in addition to the halogen atom(s),
and wherein when only one of R.sup.1 to R.sup.6 is a substituent of
Formula (2), then at least one of R.sup.1 to R.sup.6 is a
halo-substituted or unsubstituted alkyl or cycloalkyl group having
about six or less carbon atom(s) or "n" is a natural number of 2 or
more.
[0015] Such novel halophenylbiadamantane derivatives are widely
usable as materials for a wide variety of adamantane
derivative.
[0016] According to another embodiment of the present invention,
there is provided an ethynylphenylbiadamantane derivative which is
represented by following Formula (3):
##STR00005##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6
are the same as or different from one another and each represent a
hydrogen atom, a halo-substituted or unsubstituted alkyl or
cycloalkyl group having about six or less carbon atom(s), a
substituted or unsubstituted phenyl group, a carboxyl group, a
substituted or unsubstituted carbamoyl group, a substituted
oxycarbonyl group, a substituted or unsubstituted amino group, a
halogen atom, or a hydroxyl group, with the proviso that at least
one of R.sup.1 to R.sup.6 represents a substituent represented by
following Formula (4):
##STR00006##
wherein Y represents a hydrogen atom, an alkyl group having about
one to about six carbon atoms, a phenyl group, or a tri-substituted
silyl group; and "n" denotes a natural number of 1 to 5, wherein
when two or more of R.sup.1 to R.sup.6 represent substituents of
Formula (4), these substituents may be the same as or different
from one another, and wherein when "n" is 1 in all the
substituent(s) of Formula (4) as R.sup.1 to R.sup.6, then at least
one of R.sup.1 to R.sup.6 is a halo-substituted or unsubstituted
alkyl or cycloalkyl group having about six or less carbon
atom(s).
[0017] Such novel ethynylphenylbiadamantane derivatives are
satisfactorily soluble in solvents and are usable as starting
materials to give functional materials excellent typically in
electrical properties, thermal properties, mechanical properties,
optical properties, and/or physical properties.
[0018] According to yet another embodiment of the present
invention, there is provided a process for the preparation of
ethynylphenylbiadamantane derivatives. The process includes the
step of reacting a halophenyladamantane derivative with a terminal
alkyne to give an ethynylphenylbiadamantane derivative,
[0019] in which the halophenyladamantane derivative is represented
by following Formula (1a):
##STR00007##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6
are the same as or different from one another and each represent a
hydrogen atom, a halo-substituted or unsubstituted alkyl or
cycloalkyl group having about six or less carbon atom(s), a
substituted or unsubstituted phenyl group, a carboxyl group, a
substituted or unsubstituted carbamoyl group, a substituted
oxycarbonyl group, a substituted or unsubstituted amino group, a
halogen atom, or a hydroxyl group, with the proviso that at least
one of R.sup.1 to R.sup.6 represents a substituent represented by
following Formula (2):
##STR00008##
wherein X represents a halogen atom; and "n" denotes a natural
number of 1 to 5, wherein, when two or more of R.sup.1 to R.sup.6
represent substituents of Formula (2), these substituents may be
the same as or different from one another, wherein the benzene ring
in Formula (2) may further have an alkyl or cycloalkyl group having
about six or less carbon atoms in addition to the halogen atom(s),
and wherein when "n" is 1 in all the substituent(s) of Formula (2)
as R.sup.1 to R.sup.6, then at least one of R.sup.1 to R.sup.6 is a
halo-substituted or unsubstituted alkyl or cycloalkyl group having
about six or less carbon atom(s),
[0020] the terminal alykyne is represented by following Formula
(5):
R'--C .ident.C--Y (5)
wherein Y represents a hydrogen atom, an alkyl group having about
one to about six carbon atoms, a phenyl group, or a tri-substituted
silyl group; and R' represents a hydrogen atom or a metal atom,
and
[0021] the ethynylphenylbiadamantane derivative is represented by
following Formula (3):
##STR00009##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6
are the same as or different from one another and each represent a
hydrogen atom, a halo-substituted or unsubstituted alkyl or
cycloalkyl group having about six or less carbon atom(s), a
substituted or unsubstituted phenyl group, a carboxyl group, a
substituted or unsubstituted carbamoyl group, a substituted
oxycarbonyl group, a substituted or unsubstituted amino group, a
halogen atom, or a hydroxyl group, with the proviso that at least
one of R.sup.1 to R.sup.6 represents a substituent represented by
following Formula (4):
##STR00010##
wherein Y represents a hydrogen atom, an alkyl group having about
one to about six carbon atoms, a phenyl group, or a tri-substituted
silyl group; and "n" denotes a natural number of 1 to 5, wherein
when two or more of R.sup.1 to R.sup.6 represent substituents of
Formula (4), these substituents may be the same as or different
from one another, wherein when "n" is 1 in all the substituent(s)
of Formula (4) as R.sup.1 to R.sup.6, then at least one of R.sup.1
to R.sup.6 is a halo-substituted or unsubstituted alkyl or
cycloalkyl group having about six or less carbon atom(s).
[0022] In addition and advantageously, there is provided another
process for the preparation of ethynylphenylbiadamantane
derivatives. This process includes the step of reacting an
ethynylphenylbiadamantane derivative (3a) with an alcohol compound
to give another ethynylphenylbiadamantane derivative (3b),
[0023] in which the ethynylphenylbiadamantane derivative (3a) is
represented by following Formula (3a):
##STR00011##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6
are the same as or different from one another and each represent a
hydrogen atom, a halo-substituted or unsubstituted alkyl or
cycloalkyl group having about six or less carbon atom(s), a
substituted or unsubstituted phenyl group, a carboxyl group, a
substituted or unsubstituted carbamoyl group, a substituted
oxycarbonyl group, a substituted or unsubstituted amino group, a
halogen atom, or a hydroxyl group, with the proviso that at least
one of R.sup.1 to R.sup.6 represents a substituent represented by
following Formula (4a):
##STR00012##
wherein Y represents a tri-substituted silyl group; and "n" denotes
a natural number of 1 to 5, wherein when two or more of R.sup.1 to
R.sup.6 represent substituents of Formula (4a), these substituents
may be the same as or different from one another, wherein when "n"
is 1 in all the substituent(s) of Formula (4a) as R.sup.1 to
R.sup.6, then at least one of R.sup.1 to R.sup.6 is a
halo-substituted or unsubstituted alkyl or cycloalkyl group having
about six or less carbon atom(s) or and
[0024] the ethynylphenylbiadamantane derivative (3b) is represented
by following Formula (3b):
##STR00013##
wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6
are the same as or different from one another and each represent a
hydrogen atom, a halo-substituted or unsubstituted alkyl or
cycloalkyl group having about six or less carbon atom(s), a
substituted or unsubstituted phenyl group, a carboxyl group, a
substituted or unsubstituted carbamoyl group, a substituted
oxycarbonyl group, a substituted or unsubstituted amino group, a
halogen atom, or a hydroxyl group, with the proviso that at least
one of R.sup.1 to R.sup.6 represents a substituent represented by
following Formula (4b):
##STR00014##
wherein "n" denotes a natural number of 1 to 5, wherein when two or
more of R.sup.1 to R.sup.6 represent substituents of Formula (4b),
these substituents may be the same as or different from one
another, wherein when "n" is 1 in all the substituents(s)
represented by Formula (4b) as R.sup.1 to R.sup.6, then at least
one of R.sup.1 to R.sup.6 is a halo-substituted or unsubstituted
alkyl or cycloalkyl group having about six or less carbon
atom(s).
[0025] According to these processes, ethynylphenylbiadamantane
derivatives can be industrially efficiently prepared from
halophenylbiadamantane derivatives.
[0026] These and other objects, features, and advantages of the
present invention will be more fully understood from the following
description of preferred embodiments. As used herein, the term
"alkyl or cycloalkyl group" refers to an alkyl group, a cycloalkyl
group, or a group composed of an alkyl group and a cycloalkyl group
bonded to each other. All numbers are herein assumed to be modified
by the term "about."
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Halophenylbiadamantane Derivatives
[0027] Halophenylbiadamantane derivatives according to embodiments
of the present invention are represented by Formula (1). In Formula
(1), R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6 are
the same as or different from one another and each represent a
hydrogen atom, a halo-substituted or unsubstituted alkyl or
cycloalkyl group having about six or less carbon atom(s), a
substituted or unsubstituted phenyl group, a carboxyl group, a
substituted or unsubstituted carbamoyl group, a substituted
oxycarbonyl group, a substituted or unsubstituted amino group, a
halogen atom, or a hydroxyl group, with the proviso that at least
one of R.sup.1 to R.sup.6 represents a substituent of Formula (2).
In Formula (2), X represents a halogen atom; and "n" denotes a
natural number of 1 to 5.
[0028] When two or more of R.sup.1 to R.sup.6 are substituents of
Formula (2), these substituents may be the same as or different
from one another. The benzene ring in Formula (2) may further have
an alkyl or cycloalkyl group having about six or less carbon atoms
in addition to the halogen atom(s). When only one of R.sup.1 to
R.sup.6 is a substituent of Formula (2), then at least one of
R.sup.1 to R.sup.6 is a halo-substituted or unsubstituted alkyl or
cycloalkyl group having about six or less carbon atom(s) or "n" is
a natural number of 2 or more.
[0029] As R.sup.1 to R.sup.6, the halo-substituted or unsubstituted
alkyl or cycloalkyl groups each having about six or less carbon
atom(s) can be any groups that have an activity of improving the
solubility. Exemplary halo-substituted or unsubstituted alkyl
groups having about six or less carbon atom(s) include linear or
branched alkyl groups having about one to about six carbon atoms,
such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl,
t-butyl, pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl,
3-methylbutyl, hexyl, 4-methylpentyl, 1,3-dimethylbutyl,
1,1-dimethylbutyl, 2-methylpentyl, 3,3-dimethylbutyl,
1,2,2-trimethylpropyl, and 2,2-dimethylbutyl groups; and groups
corresponding to these groups, except with at least one halogen
atom replacing at least one hydrogen atom thereof.
[0030] Exemplary halo-substituted or unsubstituted cycloalkyl
groups having about six or less carbon atom(s) as R.sup.1 to
R.sup.6 include cycloalkyl groups having about three to about six
members, such as cyclopropyl, cyclobutyl, cyclopentyl, and
cyclohexyl groups, of which cycloalkyl groups having five or six
members are preferred; and groups corresponding to these groups,
except with at least one halogen atom replacing at least one
hydrogen atom thereof.
[0031] As used herein, the term "alkyl or cycloalkyl group" further
includes a group composed of an alkyl group and a cycloalkyl group
bonded to each other. Exemplary halo-substituted or unsubstituted
groups each containing an alkyl group and a cycloalkyl group bonded
to each other having about six or less carbon atom(s) as R.sup.1 to
R.sup.6 include cyclopropylmethyl, cyclopropylethyl,
cyclopropylpropyl, 2-methyl-3-ethylcyclopropyl, 2-cyclopropylethyl,
1-ethyl-1-cyclobutyl, 2-cyclobutylethyl, 2,3-dimethylcyclobutyl,
2-ethylcyclobutyl, and cyclopentylmethyl groups; and groups
corresponding to these groups, except for having at least one
halogen atom replacing at least one hydrogen atom thereof.
[0032] The alkyl groups, cycloalkyl groups, and groups each
containing an alkyl group and a cycloalkyl group bonded to each
other may each have one or more halogen atoms. Exemplary halogen
atoms include bromine atom (Br), iodine atom (I), chlorine atom
(Cl), and fluorine atom (F).
[0033] Exemplary substituents of the substituted or unsubstituted
phenyl groups as R.sup.1 to R.sup.6 include a wide variety of
substituents including alkyl groups, cycloalkyl groups, halogen
atoms (e.g., fluorine atom, chlorine atom, bromine atom, and iodine
atom), hydroxyl group, substituted oxy groups (e.g., alkoxy groups,
aryloxy groups, aralkyloxy groups, and acyloxy groups), carboxyl
group, substituted oxycarbonyl groups (e.g., alkoxycarbonyl groups,
aryloxycarbonyl groups, and aralkyloxycarbonyl groups), substituted
or unsubstituted carbamoyl groups, cyano group, nitro group,
substituted or unsubstituted amino groups, sulfo group, and
heterocyclic groups. The hydroxyl group and carboxyl group as
substituents may be protected by any of protecting groups generally
used in organic syntheses. The substituted or unsubstituted phenyl
group is preferably phenyl group or methylphenyl group.
[0034] Exemplary substituted oxycarbonyl groups as R.sup.1 to
R.sup.6 include alkoxycarbonyl groups including alkoxycarbonyl
groups whose alkoxy moiety has about one to six carbon atoms, such
as methoxycarbonyl and ethoxycarbonyl groups; aryloxycarbonyl
groups such as phenoxycarbonyl group; and aralkyloxycarbonyl groups
such as benzyloxycarbonyl group.
[0035] Exemplary substituted or unsubstituted carbamoyl groups as
R.sup.1 to R.sup.6 include unsubstituted carbamoyl group; and
carbamoyl groups having a variety of substituents. Such
substituents include alkyl groups such as methyl, ethyl, propyl,
isopropyl, n-butyl, s-butyl, and t-butyl groups; and acyl groups
such as acetyl and benzoyl groups.
[0036] Exemplary substituted or unsubstituted amino groups as
R.sup.1 to R.sup.6 include unsubstituted amino group; and amino
groups having a variety of substituents. Such substituents include
alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl,
s-butyl, and t-butyl groups; and acyl groups such as acetyl and
benzoyl groups.
[0037] The carboxyl group and hydroxyl group as R.sup.1 to R.sup.6
may each be protected by any of protecting groups generally used in
organic syntheses.
[0038] In a preferred embodiment, at least one (more preferably two
or four) of R.sup.1 to R.sup.6 is a linear alkyl group or
cycloalkyl group having about six or less carbon atom(s). This
further improves the solubility in solvents as the monomer
(halophenylbiadamantane derivative) and improves the solubility in
solvents as a polymer polymerized from the monomer.
[0039] In the substituent of Formula (2), X represents a halogen
atom; and "n" denotes a natural number of 1 to 5. The benzene ring
in Formula (2) may further have an alkyl or cycloalkyl group having
about six or less carbon atoms, in addition to the halogen atom(s).
Exemplary halogen atoms and exemplary alkyl or cycloalkyl groups
each having about six or less carbon atoms(s) are as above.
[0040] Exemplary substituents of Formula (2) which have one or more
halogen atoms include monobromophenyl groups such as 2-bromophenyl,
3-bromophenyl, and 4-bromophenyl; dibromophenyl groups such as
2,3-dibromophenyl, 2,4-dibromophenyl, 2,5-dibromophenyl, and
3,5-dibromophenyl; tribromophenyl groups such as
2,3,4-tribromophenyl, 3,4,5-tribromophenyl, 2,3,5-tribromophenyl,
and 2,3,6-tribromophenyl; and tetrabromophenyl groups such as
2,3,4,5-tetrabromophenyl and 2,3,5,6-tetrabromophenyl.
[0041] Exemplary substituents of Formula (2) which have one or more
alkyl groups in addition to one or more halogen atoms include
monobromophenyl groups such as 3-methyl-2-bromophenyl,
4-methyl-2-bromophenyl, 5-methyl-2-bromophenyl,
6-methyl-2-bromophenyl, 2-methyl-3-bromophenyl,
4-methyl-3-bromophenyl, 5-methyl-3-bromophenyl,
6-methyl-3-bromophenyl, 2-methyl-4-bromophenyl, and
3-methyl-4-bromophenyl; dibromophenyl groups such as
4-methyl-2,3-dibromophenyl, 5-methyl-2,3-dibromophenyl,
6-methyl-2,3-dibromophenyl, 3-methyl-2,4-dibromophenyl,
5-methyl-2,4-dibromophenyl, 6-methyl-2,4-dibromophenyl,
3-methyl-2,5-dibromophenyl, 4-methyl-2,5-dibromophenyl,
6-methyl-2,5-dibromophenyl, 2-methyl-3,5-dibromophenyl, and
4-methyl-3,5-dibromophenyl; tribromophenyl groups such as
5-methyl-2,3,4-tribromophenyl, 6-methyl-2,3,4-tribromophenyl,
2-methyl-3,4,5-tribromophenyl, 4-methyl-2,3,5-tribromophenyl,
6-methyl-2,3,5-tribromophenyl, 4-methyl-2,3,6-tribromophenyl, and
5-methyl-2,3,6-tribromophenyl; and tetrabromophenyl groups such as
6-methyl-2,3,4,5-tetrabromophenyl and
4-methyl-2,3,4,5-tetrabromophenyl.
[0042] Exemplary substituents of Formula (2) further include groups
corresponding to the above-exemplified groups, except for having
iodine atom (I), chlorine atom (Cl), and/or fluorine atom (F) as
the halogen atom instead of the bromine atom (Br). In addition,
exemplary substituents of Formula (2) further include groups
corresponding to the above-exemplified groups, except for having
one or more other alkyl or cycloalkyl groups having about six or
less carbon atom(s) as mentioned above, instead of the methyl
group.
[0043] Representative halophenylbiadamantane derivatives of Formula
(1), in which all of R.sup.1 to R.sup.6 are each a hydrogen atom or
a substituent of Formula (2), include
3-(3,5-dibromophenyl)-1,1'-biadamantane,
3,3-di(4-bromophenyl)-1,1'-biadamantane,
3,3-di(3,5-dibromophenyl)-1,1'-biadamantane,
3,3',5-tri(4-bromophenyl)-1,1'-biadamantane,
3,3',5-tri(3,5-dibromophenyl)-1,1'-biadamantane,
3,3',5,5'-tetra(4-bromophenyl)-1,1'-biadamantane, and
3,3',5,5'-tetra(3,5-dibromophenyl)-1,1'-biadamantane.
[0044] Representative halophenylbiadamantane derivatives of Formula
(1), in which all of R.sup.1 to R.sup.6 are each a hydrogen atom or
a substituent of Formula (2), further include compounds
corresponding to the above-exemplified compounds, except for having
iodine atom (I), chlorine atom (Cl), and/or fluorine atom (F) as
the halogen atom instead of the bromine atom (Br).
[0045] Representative halophenylbiadamantane derivatives of Formula
(1), in which at least one of R.sup.1 to R.sup.6 is an alkyl or
cycloalkyl group having about six or less carbon atom(s) and at
least one of R.sup.1 to R.sup.6 is a substituent of Formula (2),
include biadamantane derivatives having methyl group as the alkyl
or cycloalkyl group having about six or less carbon atom(s), such
as 3-(4-bromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3-(3,5-dibromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3,3'-bis(4-bromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane,
and
3,3'-bis(3,5-dibromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane;
biadamantane derivatives having ethyl group as the alkyl or
cycloalkyl group having about six or less carbon atom(s), such as
3-(4-bromophenyl)-5,5',7,7'-tetraethyl-1,1'-biadamantane,
3-(3,5-dibromophenyl)-5,5',7,7'-tetraethyl-1,1'-biadamantane,
3,3'-bis(4-bromophenyl)-5,5',7,7'-tetraethyl-1,1'-biadamantane, and
3,3'-bis(3,5-dibromophenyl)-5,5',7,7'-tetraethyl-1,1'-biadamantane;
and halophenylbiadamantane derivatives having n-butyl group as the
alkyl or cycloalkyl group having about six or less carbon atom(s),
such as
3-(4-bromophenyl)-5,5',7,7'-tetra(n-butyl)-1,1'-biadamantane,
3-(3,5-dibromophenyl)-5,5',7,7'-tetrakis(n-butyl)-1,1'-biadamantane,
3,3'-bis(4-bromophenyl)-5,5',7,7'-tetrakis(n-butyl)-1,1'-biadamantane,
and
3,3'-bis(3,5-dibromophenyl)-5,5',7,7'-tetrakis(n-butyl)-1,1'-biadaman-
tane.
[0046] Exemplary halophenylbiadamantane derivatives of Formula (1),
in which at least one of R.sup.1 to R.sup.6 is an alkyl or
cycloalkyl group having about six or less carbon atom(s) and at
least one of them is a substituent of Formula (2), further include
compounds corresponding to the above-exemplified compounds, except
for having iodine atom (I), chlorine atom (Cl), and/or fluorine
atom (F) as the halogen atom instead of the bromine atom (Br).
[0047] Representative halophenylbiadamantane derivatives of Formula
(1), in which all of R.sup.1 to R.sup.6 are each a hydrogen atom or
a substituent of Formula (2) and the benzene ring in Formula (2)
has an alkyl or cycloalkyl group having about six or less carbon
atom(s) in addition to the halogen atom(s), include
3-(4-methyl-3,5-dibromophenyl)-1,1'-biadamantane,
3-(2-methyl-3,5-dibromophenyl)-1,1'-biadamantane,
3,3'-bis(2-methyl-4-bromophenyl)-1,1'-biadamantane,
3,3'-bis(3-methyl-4-bromophenyl)-1,1'-biadamantane,
3,3'-bis(4-methyl-3,5-dibromophenyl)-1,1'-biadamantane,
3,3'-bis(2-methyl-3,5-dibromophenyl)-1,1'-biadamantane,
3,3',5-tris(2-methyl-4-bromophenyl)-1,1'-biadamantane,
3,3',5-tris(3-methyl-4-bromophenyl)-1,1'-biadamantane,
3,3',5-tris(4-methyl-3,5-dibromophenyl)-1,1'-biadamantane,
3,3',5-tris(2-methyl-3,5-dibromophenyl)-1,1'-biadamantane,
3,3',5,5'-tetrakis(2-methyl-4-bromophenyl)-1,1'-biadamantane,
3,3',5,5'-tetrakis(3-methyl-4-bromophenyl)-1,1-adamantane,
3,3',5,5'-tetrakis(4-methyl-3,5-dibromophenyl)-1,1'-biadamantane,
and
3,3',5,5'-tetrakis(2-methyl-3,5-dibromophenyl)-1,1'-biadamantane.
[0048] Exemplary halophenylbiadamantane derivatives of Formula (1),
in which all of R.sup.1 to R.sup.6 are each a hydrogen atom or a
substituent of Formula (2) and the benzene ring in Formula (2) has
an alkyl or cycloalkyl group having about six or less carbon
atom(s) in addition to the halogen atom(s), further include
compounds corresponding to the above-exemplified compounds, except
for having iodine atom (I), chlorine atom (Cl), and/or fluorine
atom (F) as the halogen atom instead of the bromine atom (Br). The
exemplary halophenylbiadamantane derivatives just mentioned above
further include compounds corresponding to the above-exemplified
compounds, except for having one or more other alkyl or cycloalkyl
groups having about six or less carbon atom(s) as mention above,
instead of the methyl group.
[0049] Representative halophenylbiadamantane derivatives of Formula
(1), in which at least one of R.sup.1 to R.sup.6 is an alkyl or
cycloalkyl group having about six or less carbon atom(s) and at
least one of R.sup.1 to R.sup.6 is a substituent of Formula (2) and
the benzene ring in Formula (2) has one or more halogen atoms and
one or more alkyl groups, include biadamantane derivatives, in
which at least one of R.sup.1 to R.sup.6 is methyl group as the
alkyl or cycloalkyl group having about six or less carbon atom(s),
such as
3-(2-methyl-4-bromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3-(3-methyl-4-bromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3-(2-methyl-3,5-dibromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3-(4-methyl-3,5-dibromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3,3'-bis(2-methyl-4-bromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3,3'-bis(3-methyl-4-bromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3,3'-bis(2-methyl-3,5-dibromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamant-
ane, and
3,3'-bis(4-methyl-3,5-dibromophenyl)-5,5',7,7'-tetramethyl-1,1'-b-
iadamantane; biadamantane derivatives, in which at least one of
R.sup.1 to R.sup.6 is ethyl group as the alkyl or cycloalkyl group
having about six or less carbon atom(s), such as
3-(2-methyl-4-bromophenyl)-5,5',7,7'-tetraethyl-1,1'-biadamantane,
3-(3-methyl-4-bromophenyl)-5,5',7,7'-tetraethyl-1,1'-biadamantane,
3-(2-methyl-3,5-dibromophenyl)-5,5',7,7'-tetraethyl-1,1'-biadamantane,
3-(4-methyl-3,5-dibromophenyl)-5,5',7,7'-tetraethyl-1,1'-biadamantane,
3,3'-bis(2-methyl-4-bromophenyl)-5,5',7,7'-tetraethyl-1,1'-biadamantane,
3,3'-bis(3-methyl-4-bromophenyl)-5,5',7,7'-tetraethyl-1,1'-biadamantane,
3,3'-bis(2-methyl-3,5-dibromophenyl)-5,5',7,7'-tetraethyl-1,1'-biadamanta-
ne, and
3,3'-bis(4-methyl-3,5-dibromophenyl)-5,5',7,7'-tetraethyl-1,1'-bia-
damantane; and biadamantane derivatives, in which at least one of
R.sup.1 to R.sup.6 is n-butyl group as the alkyl or cycloalkyl
group having about six or less carbon atom(s), such as
3-(2-methyl-4-bromophenyl)-5,5',7,7'-tetrakis(n-butyl)-1,1'-biadamantane,
3-(3-methyl-4-bromophenyl)-5,5',7,7'-tetrakis(n-butyl)-1,1'-biadamantane,
3-(2-methyl-3,5-dibromophenyl)-5,5',7,7'-tetrakis(n-butyl)-1,1'-biadamant-
ane,
3-(2-methyl-3,5-dibromophenyl)-5,5',7,7'-tetrakis(n-butyl)-1,1'-biada-
mantane,
3,3'-bis(2-methyl-4-bromophenyl)-5,5',7,7'-tetra(n-butyl)-1,1'-bi-
adamantane,
3,3'-bis(2-methyl-4-bromophenyl)-5,5',7,7'-tetrakis(n-butyl)-1,1'-biadama-
ntane,
3,3'-bis(2-methyl-3,5-dibromophenyl)-5,5',7,7'-tetrakis(n-butyl)-1,-
1'-biadamantane, and
3,3'-bis(4-methyl-3,5-dibromophenyl)-5,5',7,7'-tetrakis(n-butyl)-1,1'-bia-
damantane.
[0050] In addition to these compounds, exemplary
halophenylbiadamantane derivatives of Formula (1) further include
compounds corresponding to the above-exemplified compounds, except
for having iodine atom (I), chlorine atom (Cl), and/or fluorine
atom (F) as the halogen atom instead of the bromine atom (Br).
[0051] Halophenylbiadamantane derivatives according to embodiments
of the present invention may each be prepared from a biadamantane
halide derivative or biadamantane alcohol derivative with an
aromatic compound or a derivative thereof as starting materials by
introducing one or more halogenated benzene rings into the
biadamantane skeleton or by introducing one or more benzene rings
and subsequently introducing one or more halogen atoms into the
biadamantane skeleton. Introduction of one or more benzene rings
into the biadamantane skeleton may be conducted typically by a
Friedel-Crafts reaction, in which a benzene ring is introduced into
a biadamantane skeleton of a biadamantane halide derivative or
biadamantane alcohol derivative as a starting material; or by a
Grignard reaction, in which a benzene ring is introduced into a
biadamantane skeleton of a biadamantane halide derivative as a
starting material. It is also acceptable that one or more halogen
atoms and/or hydroxyl groups remain in the introduced biadamantane
skeleton by adjusting the amount of the aromatic compound or by
controlling the reaction conditions such as the temperature and
amount of catalyst in the introduction process of a benzene
ring.
[0052] In the Friedel-Crafts reaction, a benzene ring can be
introduced into the biadamantane skeleton in the presence of a
Lewis acid catalyst in an electrophilic substitution manner. In the
Grignard reaction, a benzene ring can be introduced into the
biadamantane ring by a coupling reaction between an organic halide
and a Grignard reagent.
[0053] Exemplary preparation processes (schemes) of
halophenylbiadamantane derivatives according to embodiments of the
present invention are shown below. In the schemes, X represents a
halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, and
iodine atom), R.sup.1 to R.sup.6 are as defined above. However,
halophenylbiadamantane derivatives according to embodiments of the
present invention are not limited to those prepared by these
processes.
##STR00015##
[0054] Exemplary biadamantane halide derivatives for use as a
starting material include monohalobiadamantane derivatives such as
3-bromo-1,1'-biadamantane, 2-bromo-1,1'-biadamantane,
4-bromo-1,1'-biadamantane, 3-bromo-5,7-dimethyl-1,1'-biadamantane,
3-bromo-5',7'-dimethyl-1,1'-biadamantane,
3-bromo-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3-bromo-5,5',7,7'-tetraethyl-1,1'-biadamantane,
3-bromo-5,5',7,7'-tetrabutyl-1,1'-biadamantane, and
3-bromo-5,5',7,7'-tetrakis(trifluoromethyl)-1,1'-biadamantane;
dihalobiadamantane derivatives such as
3,3'-dibromo-1,1'-biadamantane, 2,3'-dibromo-1,1'-biadamantane,
3',4-dibromo-1,1'-biadamantane, 2,2'-dibromo-1,1'-biadamantane,
4,4'-dibromo-1,1'-biadamantane,
3,3'-dibromo-5,7-dimethyl-1,1'-biadamantane,
3,3'-dibromo-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3,3'-dibromo-5,5',7,7'-tetraethyl-1,1'-biadamantane,
3,3'-dibromo-5,5',7,7'-tetrabutyl-1,1'-biadamantane,
3,3'-dibromo-5,5',7,7'-tetrakis(trifluoromethyl)-1,1'-biadamantane,
3,3'-dibromo-5,5',7,7'-tetrahydroxy-1,1'-biadamantane, and
3,3'-dibromo-5,5',7,7'-tetraamino-1,1'-biadamantane;
tetrahalobiadamantane derivatives such as
3,3',5,5'-tetrabromo-1,1'-biadamantane; and hexahalobiadamantane
derivatives such as 3,3',5,5',7,7'-hexabromo-1,1'-biadamantane.
[0055] Exemplary biadamantane alcohol derivatives for use as a
starting material include monohydroxybiadamantane derivatives such
as 3-hydroxy-1,1'-biadamantane, 2-hydroxy-1,1'-biadamantane,
4-hydroxy-1,1'-biadamantane,
3-hydroxy-5,7-dimethyl-1,1'-biadamantane,
3-hydroxy-5',7'-dimethyl-1,1'-biadamantane,
3-hydroxy-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3-hydroxy-5,5',7,7'-tetraethyl-1,1'-biadamantane,
3-hydroxy-5,5',7,7'-tetrabutyl-1,1'-biadamantane, and
3-hydroxy-5,5',7,7'-tetrakis(trifluoromethyl)-1,1'-biadamantane;
dihydroxybiadamantane derivatives such as
3,3'-dihydroxy-1,1'-biadamantane, 2,3'-dihydroxy-1,1'-biadamantane,
3',4-dihydroxy-1,1'-biadamantane, 2,2'-dihydroxy-1,1'-biadamantane,
4,4'-dihydroxy-1,1'-biadamantane,
3,3'-dihydroxy-5,7-dimethyl-1,1'-biadamantane,
3,3'-dihydroxy-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3,3'-dihydroxy-5,5',7,7'-tetraethyl-1,1'-biadamantane,
3,3'-dihydroxy-5,5',7,7'-tetrabutyl-1,1'-biadamantane,
3,3'-dihydroxy-5,5',7,7'-tetrakis(trifluoromethyl)-1,1'-biadamantane,
and 3,3'-dihydroxy-5,5',7,7'-tetraamino-1,1'-biadamantane;
tetrahydroxybiadamantane derivatives such as
3,3',5,5'-tetrahydroxy-1,1'-biadamantane; and
hexahydroxybiadamantane derivatives such as
3,3',5,5',7,7'-hexahydroxy-1,1'-biadamantane.
[0056] Exemplary aromatic compounds or derivatives for use as a
starting material include bromobenzene, 1,3-dibromobenzene,
1,3,5-tribromobenzene, iodobenzene, 1,3-diiodobenzene, and
1,3,5-triiodobenzene. Among them, bromobenzene and/or
1,3-dibromobenzene is preferably used. The amount of the aromatic
compound or a derivative thereof is, for example, about 1 to 1000
moles, preferably about 2 to 500 moles, and more preferably about 5
to 200 moles, to 1 mole of the biadamantane halide derivative or
biadamantane alcohol derivative.
[0057] The Friedel-Crafts reaction is carried out in the presence
of a Lewis acid catalyst. Exemplary Lewis acid catalysts include
iron halides such as FeCl.sub.3 and FeBr.sub.3; aluminum halides
such as AlCl.sub.3 and AlBr.sub.3; zirconium halides such as
ZrCl.sub.2 and ZrCl.sub.4; and BF.sub.3. Among them, AlCl.sub.3 is
advantageously used. The amount of Lewis acid catalysts can be set
as appropriate according typically to the reaction rate and is, for
example, about 0.001 to 10 moles, and preferably about 0.05 to 5
moles, to 1 mole of the biadamantane halide derivative or
biadamantane alcohol derivative.
[0058] A Friedel-Crafts reaction, if using a biadamantane alcohol
derivative as a starting material for a halophenylbiadamantane
derivative, is preferably carried out in the presence of an acid,
so as to accelerate the reaction. Exemplary acids include inorganic
acids such as sulfuric acid, hydrochloric acid, hydrobromic acid,
nitric acid, and phosphoric acid; sulfonic acids such as
methanesulfonic acid; carboxylic acids such as acetic acid and
propionic acid; heteropolyacids; and cation-exchange resins. Among
them, preferred are strong acids including inorganic acids such as
hydrochloric acid and sulfuric acid; sulfonic acids such as
p-toluenesulfonic acid; heteropolyacids; and strongly acidic
cation-exchange resins. The amount of acids is, for example, about
0.1 to 10 moles, and preferably about 0.1 to 5 moles, to 1 mole of
the biadamantane alcohol derivative.
[0059] The Friedel-Crafts reaction is carried out in the presence
of, or in the absence of, an inert solvent. Exemplary solvents
include hydrocarbons such as hexane and cyclohexane; halogenated
hydrocarbons such as methylene chloride, 1,2-dichloroethane,
chloroform, and carbon tetrachloride; chain or cyclic ethers such
as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane;
nitriles such as acetonitrile and benzonitrile; esters such as
ethyl acetate; carboxylic acids such as acetic acid; amides such as
N,N-dimethylformamide; ketones such as acetone and methyl ethyl
ketone; nitro compounds such as nitromethane and nitrobenzene; and
mixtures of these solvents.
[0060] The reaction temperature may be suitably set according
typically to the types of reaction components. Typically, when a
biadamantane halide derivative is used, the reaction temperature
is, for example, about -50.degree. C. to 200.degree. C., preferably
about -20.degree. C. to 150.degree. C. When a biadamantane alcohol
derivative is used, the reaction temperature is, for example, about
10.degree. C. to 200.degree. C., preferably about 40.degree. C. to
150.degree. C., and more preferably about 60.degree. C. to
130.degree. C. The reaction may be conducted under normal
atmospheric pressure, under reduced pressure, or under a pressure
(under a load). The reaction atmosphere is not particularly
limited, as long as it does not adversely affect the reaction, and
can be any of, for example, air atmosphere, nitrogen atmosphere,
and argon atmosphere. The reaction may be conducted according to
any system such as a batch system, semi-batch system, or continuous
system.
[0061] In the Grignard reaction, the Grignard reagent is
synthetically prepared by a reaction between magnesium and a
halogen-containing compound. Exemplary Grignard reagents for use
herein include phenylmagnesium bromide, phenylmagnesium iodide, and
phenylmagnesium chloride, of which phenylmagnesium bromide is
preferred. These Grignard reagents may be those formed in a reactor
in situ or in another vessel or may be commercially available
products. The amount of the Grignard reagents is, for example,
about 1 to 2 moles, preferably about 1 to 1.5 moles, and more
preferably about 1 to 1.2 moles, to 1 mole of the biadamantane
halide derivative.
[0062] The Grignard reaction is carried out in a solvent. It is
preferred that the Grignard reaction is conducted in an anhydrous
or absolute ether solvent in an inert atmosphere, because this
reaction uses a Grignard reagent. Preferred exemplary ether
solvents are diethyl ether, diisopropyl ether, and tetrahydrofuran,
of which tetrahydrofuran is more preferred.
[0063] The reaction temperature may be suitably set according
typically to the types of reaction components and catalysts and is,
for example, about -20.degree. C. to 80.degree. C., and preferably
about -10.degree. C. to 50.degree. C. The reaction may be conducted
under normal atmospheric pressure, under reduced pressure, or under
a pressure (under a load). The reaction atmosphere is not
particularly limited, as long as it does not adversely affect the
reaction, and can be any of, for example, air atmosphere, nitrogen
atmosphere, and argon atmosphere. The reaction may be conducted
according to any system such as a batch system, semi-batch system,
or continuous system.
[0064] When a reaction product is obtained in a high yield after
the reaction but the reaction mixture contains an acid catalyst,
the purification of the reaction product may be conducted by a
general purification procedure for removing catalysts, such as
adjustment of pH of the reaction mixture, concentration,
filtration, and/or washing. When the reaction mixture contains
large amounts of by-products, the purification can be conducted by
a common separation and purification procedure such as
crystallization, recrystallization, or column chromatography, or
any combination of these procedures.
[0065] The crystallization is carried out by dissolving the
reaction mixture in a suitable solvent where necessary with
heating, concentrating the solution according to necessity, and
cooling the solution to precipitate crystals. Exemplary solvents
include ethers such as tetrahydrofuran; ketones such as acetone;
hydrocarbons such as toluene; halogenated hydrocarbons such as
chloroform; and mixtures of these solvents. The crystallization is
conducted, for example, by using a combination of a good solvent
(e.g., tetrahydrofuran or toluene) and a poor solvent (e.g.,
methanol) or by using a combination of water and a water-miscible
organic solvent (e.g., tetrahydrofuran, 1,4-dioxane, acetone, or
acetonitrile).
[0066] The halophenylbiadamantane derivatives according to
embodiments of the present invention excel in solubility in
solvents, and whose halogen atom can be converted into a
substituent of various kind, such as carbonyl group, alkyl group,
phenyl group, alkenyl group, or alkynyl group (e.g., ethynyl
group), and are widely usable as starting materials for a variety
of adamantane derivatives.
[0067] Ethynylphenylbiadamantane Derivatives
[0068] Ethynylphenylbiadamantane derivatives according to
embodiments of the present invention are represented by Formula
(3). In Formula (3), R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
and R.sup.6 are the same as or different from one another and each
represent a hydrogen atom, a halo-substituted or unsubstituted
alkyl or cycloalkyl group having about six or less carbon atom(s),
a substituted or unsubstituted phenyl group, a carboxyl group, a
substituted or unsubstituted carbamoyl group, a substituted
oxycarbonyl group, a substituted or unsubstituted amino group, a
halogen atom, or a hydroxyl group, with the proviso that at least
one of R.sup.1 to R.sup.6 represents a substituent of Formula (4).
In Formula (4), Y represents a hydrogen atom, an alkyl group having
about one to about six carbon atoms, a phenyl group, or a
tri-substituted silyl group; and "n" denotes a natural number of 1
to 5.
[0069] When two or more of R.sup.1 to R.sup.6 represent
substituents of Formula (4), these substituents may be the same as
or different from one another. When "n" is 1 in all the
substituent(s) of Formula (4) as R.sup.1 to R.sup.6, then at least
one of R.sup.1 to R.sup.6 is a halo-substituted or unsubstituted
alkyl or cycloalkyl group having about six or less carbon
atom(s).
[0070] In Formula (3), exemplary groups as R.sup.1 to R.sup.6 are
as with R.sup.1 to R.sup.6 in Formula (1). In Formula (4),
exemplary alkyl groups having about one to about six carbon atoms
as Y include linear or branched alkyl groups having about one to
about six carbon atoms, such as methyl, ethyl, propyl, isopropyl,
butyl, isobutyl, s-butyl, t-butyl, pentyl, 1,1-dimethylpropyl,
2,2-dimethylpropyl, 3-methylbutyl, hexyl, 4-methylpentyl,
1,3-dimethylbutyl, 1,1-dimethylbutyl, 2-methylpentyl,
3,3-dimethylbutyl, 1,2,2-trimethylpropyl, and 2,2-dimethylbutyl
groups. When Y is a tri-substituted silyl group, the three
substituents may be any of alkyl groups, cycloalkyl groups, groups
containing an alkyl group and a cycloalkyl group bonded to each
other, and phenyl group, and they may be the same as or different
from one another.
[0071] In the tri-substituted silyl group as Y, exemplary alkyl
groups as the substituents of silyl group include linear or
branched alkyl groups having about one to about six carbon atoms,
such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl,
t-butyl, pentyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl,
3-methylbutyl, hexyl, 4-methylpentyl, 1,3-dimethylbutyl,
1,1-dimethylbutyl, 2-methylpentyl, 3,3-dimethylbutyl,
1,2,2-trimethylpropyl, and 2,2-dimethylbutyl groups.
[0072] In the tri-substituted silyl group as Y, exemplary
cycloalkyl groups as the substituents of silyl group include
cycloalkyl groups having about three to about six members, such as
cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups, of
which cycloalkyl groups having about five or six members are
preferred.
[0073] In the tri-substituted silyl group as Y, exemplary groups
containing an alkyl group and a cycloalkyl group bonded to each
other as the substituents of silyl group include groups containing
an alkyl group and a cycloalkyl group having about six or less
carbon atom(s), such as cyclopropylmethyl, cyclopropylethyl,
cyclopropylpropyl, 2-methyl-3-ethylcyclopropyl, 2-cyclopropylethyl,
1-ethyl-1-cyclobutyl, 2-cyclobutylethyl, 2,3-dimethylcyclobutyl,
2-ethylcyclobutyl, and cyclopentylmethyl groups.
[0074] Exemplary ethynylphenylbiadamantane derivatives, in which
all of R.sup.1 to R.sup.6 are independently a hydrogen atom or a
group of Formula (4) and Y is a hydrogen atom, include
3-(3,5-diethynylphenyl)-1,1'-biadamantane;
3,3'-bis(3,5-diethynylphenyl)-1,1'-biadamantane; and
3,3',5,5'-tetrakis(3,5-diethynylphenyl)-1,1'-biadamantane.
[0075] Exemplary ethynylphenylbiadamantane derivatives, in which
all of R.sup.1 to R.sup.6 are independently a hydrogen atom or a
group of Formula (4) and Y is a trimethylsilyl group, include
3-(3,5-bis(trimethylsilylethynyl)phenyl)-1,1'-biadamantane;
3,3'-bis(3,5-bis(trimethylsilylethynyl)phenyl)-1,1'-biadamantane;
and
3,3',5,5'-tetrakis(3,5-bis(trimethylsilylethynyl)phenyl)-1,1'-biadamantan-
e.
[0076] Exemplary ethynylphenylbiadamantane derivatives, in which
all of R.sup.1 to R.sup.6 are independently a hydrogen atom or a
group of Formula (4) and Y is a tri-substituted silyl group,
include compounds corresponding to the above-exemplified
ethynylphenylbiadamantane derivatives, except with any of the
above-exemplified substituents of silyl group instead of the methyl
group.
[0077] Exemplary ethynylphenylbiadamantane derivatives, in which
all of R.sup.1 to R.sup.6 are independently a hydrogen atom or a
group of Formula (4) and Y is a phenyl group, include
3-(3,5-bis(phenylethynyl)phenyl)-1,1'-biadamantane;
3,3'-bis(3,5-bis(phenylethynyl)phenyl)-1,1'-biadamantane; and
3,3',5,5'-tetrakis(3,5-bis(phenylethynyl)phenyl)-1,1'-biadamantane.
[0078] Exemplary ethynylphenylbiadamantane derivatives, in which at
least one of R.sup.1 to R.sup.6 is an alkyl or cycloalkyl group
having about six or less carbon atom(s) and at least one of them is
a substituent of Formula (4), and Y is a hydrogen atom, include
3-(4-ethynylphenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3,3'-bis(4-ethynylphenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane;
3-(3,5-diethynylphenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane;
and
3,3'-bis(3,5-diethynylphenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane.
[0079] Exemplary ethynylphenylbiadamantane derivatives, in which at
least one of R.sup.1 to R.sup.6 is an alkyl or cycloalkyl group
having about six or less carbon atom(s) and at least one of them is
a substituent of Formula (4), and Y is a trimethylsilyl group,
include
3-(4-(trimethylsilylethynyl)phenyl)-5,5',7,7'-tetramethyl-1,1'-biadamanta-
ne,
3,3'-bis(4-(trimethylsilylethynyl)phenyl)-5,5',7,7'-tetramethyl-1,1'-b-
iadamantane;
3-(3,5-bis(trimethylsilylethynyl)phenyl)-5,5',7,7'-tetramethyl-1,1'-biada-
mantane; and
3,3'-bis(3,5-bis(trimethylsilylethynyl)phenyl)-5,5',7,7'-tetramethyl-1,1'-
-biadamantane.
[0080] Exemplary ethynylphenylbiadamantane derivatives, in which at
least one of R.sup.1 to R.sup.6 is an alkyl or cycloalkyl group
having about six or less carbon atom(s) and at least one of them is
a substituent of Formula (4), and Y is a phenyl group, include
3-(4-(phenylethynyl)phenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane,
3,3'-bis(4-(phenylethynyl)phenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane-
;
3-(3,5-bis(phenylethynyl)phenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane-
; and
3,3'-bis(3,5-bis(phenylethynyl)phenyl)-5,5',7,7'-tetramethyl-1,1'-bi-
adamantane.
[0081] Exemplary ethynylphenylbiadamantane derivatives, in which at
least one of R.sup.1 to R.sup.6 is an alkyl or cycloalkyl group
having about six or less carbon atom(s) and at least one of them is
a substituent of Formula (4) further include compounds
corresponding to the above-exemplified ethynylphenylbiadamantane
derivatives, except for having one or more other alkyl or
cycloalkyl groups having about six or less carbon atom(s) as
mentioned above, instead of the methyl group.
[0082] Process (1) for the Preparation of Ethynylphenylbiadamantane
Derivatives
[0083] A process according to an embodiment of the present
invention is a process for the preparation of an
ethynylphenylbiadamantane derivative of Formula (3) from a
halophenylbiadamantane derivative of Formula (1a) and a terminal
alkyne of Formula (5) as starting materials through a cross
coupling reaction (Sonogashira reaction). Such
ethynylphenylbiadamantane derivatives of Formula (3) can also be
prepared through a coupling reaction between a
halophenylbiadamantane derivative of Formula (1a) and a copper
acetylide (Castro reaction).
[0084] In the cross coupling reaction (Sonogashira reaction), a
halophenylbiadamantane derivative of Formula (1a) and a terminal
alkyne of Formula (5) are reacted through a cross coupling reaction
in the presence typically of a palladium catalyst, a copper salt as
a promoter, a ligand, and/or a basic compound, to give an
ethynylphenylbiadamantane derivative of Formula (3). The copper
salt and ligand may be used or not used in the reaction. In a
preferred embodiment, they are used in the reaction, to proceed the
reaction under milder conditions.
[0085] In Formula (5), R' represents a hydrogen atom or a metal
atom such as copper, zinc, or tin. Y in Formula (5) corresponds to
Y in the ethynylphenylbiadamantane derivative of Formula (3) and
examples of the former Y are as with the latter Y. In a preferred
embodiment, the terminal alkyne of Formula (5) is a
mono-substituted acetylene. In a more preferred embodiment, the
mono-substituted acetylene is trimethylsilylacetylene,
phenylacetylene, and/or adamantylacetylene. Exemplary terminal
alkynes further include an alkynyl copper, an alkynyl zinc, and an
alkynyl tin.
[0086] The amount of the terminal alkyne of Formula (5) is, for
example, about 1.0 to 2.0 moles, preferably about 1.0 to 1.5 moles,
and more preferably about 1.0 to 1.2 moles, to 1 mole of halogen
atoms in the halophenylbiadamantane derivative of Formula (1a).
[0087] Exemplary palladium catalysts for use herein include
inorganic compounds including elementary palladium (metal),
palladium oxides, palladium sulfides, palladium hydroxides,
palladium halides (fluoride, chloride, bromide, and iodide),
palladium sulfates, and inorganic palladium complexes; and organic
compounds such as palladium cyanides, palladium salts of organic
acids (e.g., acetates), and organic palladium complexes. Among
them, preferred are palladium halides such as palladium chloride,
palladium bromide, and palladium iodide; and palladium
complexes.
[0088] Exemplary ligands of complexes include known lignans such as
triphenylphosphine, trialkylphosphine, tricyanophenylphosphine,
tri-O-toluoylphosphine, and acetic acid, of which
triphenylphosphine is preferred.
[0089] Exemplary palladium complexes include
dichlorobis(triphenylphosphine)palladium,
dibromobis(triphenylphosphine)palladium,
diiodobis(triphenylphosphine)palladium,
dichlorobis(trimethylphosphine)palladium,
dibromobis(trimethylphosphine)palladium,
diiodobis(trimethylphosphine)palladium,
dichlorobis(tricyanophenylphosphine)palladium,
dibromobis(tricyanophenylphosphine)palladium,
diiodobis(tricyanophenylphosphine)palladium,
dichlorotetrakis(triphenylphosphine)palladium,
dibromotetrakis(triphenylphosphine)palladium, and
diiodotetrakis(triphenylphosphine)palladium. Each of these
palladium catalysts can be used alone or in combination.
[0090] The palladium catalysts can be used as intact or as
supported by a carrier (support). Exemplary carriers include those
commonly used for supporting catalysts, including inorganic metal
oxides such as silica, alumina, silica-alumina, zeolite, titania,
and magnesia; and activated carbons. The amount of palladium
catalysts, if supported by a carrier, is for example, about 0.1 to
50 percent by weight, and preferably about 1 to 20 percent by
weight, to the amount of the carrier. Supporting of the catalysts
may be conducted according to a common procedure such as
impregnation, precipitation, or ion-exchanging.
[0091] The amount of palladium catalysts is, for example, about
0.0001 to 10 moles, preferably about 0.001 to 1 mole, and more
preferably about 0.002 to 0.5 moles, to 1 mole of halogen atoms in
the halophenylbiadamantane derivative of Formula (1a) used as a
reaction component.
[0092] In a preferred embodiment, triphenylphosphine and/or
tricyanophenylphosphine are used as the ligand. The amount of the
ligand is, for example, about 0.0001 to 50 moles, preferably about
0.001 to 20 moles, and more preferably about 0.002 to 10 moles, to
1 mole of halogen atoms in the halophenylbiadamantane derivative of
Formula (1a).
[0093] Exemplary basic compounds include alkylamines such as
trimethylamine, triethylamine, diethylamine, diisopropylamine,
n-butylamine, ethylenediamine, and dimethylaminopropionitrile
(DMAP); aromatic amine compounds such as aniline; heteroaromatic
amine compounds such as pyridine, and picoline; cyclic amines such
as diazabicycloundecene and piperidine; aminoalcohols such as
ethanolamine and diethanolamine; and inorganic bases such as sodium
bicarbonate and potassium carbonate. Each of these basic compounds
can be used alone or in combination. The amount of basic compounds
is, for example, about 1 to 1000 moles, and preferably about 1 to
500 moles, to 1 mole of halogen atoms in the halophenylbiadamantane
derivative of Formula (1a).
[0094] Exemplary copper salts include copper halides such as copper
fluoride, copper chloride, copper bromide, and copper iodide. Each
of these copper salts can be used alone or in combination. The
amount of copper salts is, for example, about 0.0001 to 10 moles,
preferably about 0.001 to 1 mole, and more preferably about 0.002
to 0.5 moles, to 1 mole of halogen atoms in the
halophenylbiadamantane derivative of Formula (1a).
[0095] In the Sonogashira reaction, the reaction is carried out in
the presence of, or in the absence of, a solvent. Exemplary
solvents include hydrocarbons such as hexane, heptane, and
cyclohexane; aromatic hydrocarbons such as benzene, toluene,
xylenes, and mesitylene; halogenated hydrocarbons such as methylene
chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride;
chain or cyclic ethers such as diethyl ether, dimethoxyethane,
tetrahydrofuran, dioxolane, and diethylene glycol dimethyl ether
(diglyme); nitrites such as acetonitrile and benzonitrile; esters
such as ethyl acetate and butyl acetate; amides such as
N,N-dimethylformamide, N,N-dimethylacetamide, and
N-methyl-2-pyrrolidone; ketones such as acetone, methyl ethyl
ketone, and cyclohexanone; and nitro compounds such as nitromethane
and nitrobenzene. Each of these solvents can be used alone or in
combination. Among them, toluene, xylenes, tetrahydrofuran,
N,N-dimethylformamide, and N,N-dimethylacetamide are preferred for
better solubility. The amount of solvents is, for example, about
0.1 to 1000 parts by weight, and preferably about 1 to 100 parts by
weight, to 1 part by weight of the halophenylbiadamantane
derivative of Formula (1a).
[0096] The reaction temperature may be suitably set according
typically to the type of the halophenylbiadamantane derivative used
as a starting material, and the reaction rate, and is generally
about -20.degree. C. to 200.degree. C., preferably about
-10.degree. C. to 150.degree. C., and more preferably about
0.degree. C. to 130.degree. C.
[0097] The reaction may be conducted under normal atmospheric
pressure, under reduced pressure, or under a pressure (under a
load). The reaction atmosphere is not particularly limited, as long
as it does not adversely affect the reaction, and can be any of,
for example, air atmosphere, nitrogen atmosphere, and argon
atmosphere. The reaction may be conducted according to any system
such as a batch system, semi-batch system, or continuous system. In
a preferred embodiment, the reaction is conducted by mixing the
halophenylbiadamantane derivative as a starting material and other
components such as a palladium catalyst, a copper salt, a ligand,
and a basic compound with a solvent to give a mixture, and adding
the terminal alkyne dropwise to the mixture.
[0098] The reaction product may be separated and purified by a
procedure such as concentration, crystallization, filtration,
washing, recrystallization, precipitation, reprecipitation,
extraction, or column chromatography, or any combination of these
procedures. Typically, the catalyst, salt, and other unnecessary
components may be separated after the completion of reaction by
filtration or by adding water and an organic solvent separable from
water (e.g., toluene, xylenes, ethyl acetate, or heptane) to the
reaction mixture and conducting solution washing. When the reaction
mixture contains large amounts of by-products, the reaction product
may be separated and purified using a common separation and
purification procedure such as crystallization, recrystallization,
and/or column chromatography.
[0099] The crystallization is carried out by dissolving the
reaction mixture in a suitable solvent where necessary with
heating, concentrating the solution according to necessity, and
cooling the solution to precipitate crystals. Exemplary solvents
include ethers such as tetrahydrofuran; ketones such as acetone;
hydrocarbons such as toluene; halogenated hydrocarbons such as
chloroform; alcohols such as ethanol; and mixtures of these
solvents. The crystallization is conducted, for example, by using a
combination of a good solvent (e.g., toluene) and a poor solvent
(e.g., acetone or methanol), or by using a combination of water and
a water-miscible organic solvent (e.g., tetrahydrofuran,
1,4-dioxane, acetone, methanol, ethanol, butanol, or
acetonitrile).
[0100] In the Castro reaction, a copper acetylide and a
halophenylbiadamantane derivative of Formula (1a) are reacted with
heating in the presence of pyridine or N,N-dimethylformamide, to
give a corresponding ethynylphenylbiadamantane derivative of
Formula (3).
[0101] The copper acetylide may have, as substituents on its
ethynyl group, copper atom and any of the substituent as mentioned
above as the substituents in Y. Exemplary copper acetylides include
trimethylsilylacetylene copper and phenylacetylene copper.
[0102] The amount of copper acetylides is, for example, about 1 to
10 moles, and preferably about 1.2 to 5 moles, to 1 mole of the
halophenylbiadamantane derivative of Formula (1a). The reaction
temperature is typically about 0.degree. C. to 200.degree. C., and
preferably about 50.degree. C. to 150.degree. C.
[0103] The reaction may be conducted under normal atmospheric
pressure, under reduced pressure, or under a pressure (under a
load). The reaction atmosphere is not particularly limited, as long
as it does not adversely affect the reaction, and can be any of,
for example, air atmosphere, nitrogen atmosphere, and argon
atmosphere. The reaction may be conducted according to any system
such as a batch system, semi-batch system, or continuous
system.
[0104] The reaction product may be separated and purified by a
procedure such as concentration, crystallization, filtration,
washing, recrystallization, precipitation, reprecipitation,
extraction, or column chromatography, or any combination of these
procedures. Typically, the catalyst, salt, and other unnecessary
components may be separated after the completion of reaction by
filtration or by adding water and an organic solvent separable from
water (e.g., toluene, xylene, ethyl acetate, or heptane) to the
reaction mixture and conducing solution washing. When the reaction
mixture contains large amounts of by-products, the reaction product
may be separated and purified using a common separation and
purification procedure such as crystallization, recrystallization,
and/or column chromatography.
[0105] The crystallization is carried out by dissolving the
reaction mixture in a suitable solvent where necessary with
heating, concentrating the solution according to necessity, and
cooling the solution to precipitate crystals. Exemplary solvents
include ethers such as tetrahydrofuran; ketones such as acetone;
hydrocarbons such as toluene; halogenated hydrocarbons such as
chloroform; alcohols such as ethanol; and mixtures of these. The
crystallization is conducted, for example, by using a combination
of a good solvent (e.g., toluene) and a poor solvent (e.g., acetone
or methanol), by using a combination of water and a water-miscible
organic solvent (e.g., tetrahydrofuran, 1,4-dioxane, acetone,
methanol, ethanol, butanol, or acetonitrile).
[0106] Process (2) for the Preparation of Ethynylphenylbiadamantane
Derivatives
[0107] An ethynylphenylbiadamantane derivative of Formula (3b) is
prepared by reacting an ethynylphenylbiadamantane derivative of
Formula (3a) having a protecting silyl group with an alcohol in the
presence of a base to deprotect (remove) the protecting silyl
group.
[0108] Exemplary bases include common inorganic bases including
carbonates of alkali metals, such as potassium carbonate and sodium
carbonate; hydroxides of alkali metals, such as sodium hydroxide
and potassium hydroxide; and hydrogen carbonates of alkali metals,
such as sodium hydrogen carbonate. The amount of bases is, for
example, about 0.0001 to 10 moles, preferably about 0.001 to 1
mole, and more preferably about 0.001 to 0.5 moles, to 1 mole of
silicon atoms in the ethynylphenylbiadamantane derivative of
Formula (3a).
[0109] Exemplary alcohols to be reacted with the
ethynylphenylbiadamantane derivative of Formula (3a) include
primary alcohols, secondary alcohols, and tertiary alcohols. Each
of these alcohols may one or more hydroxyl groups and can be any of
monohydric alcohols, dihydric alcohols, and polyhydric
alcohols.
[0110] Representative primary alcohols include saturated or
unsaturated aliphatic primary alcohols having about one to thirty
carbon atoms, such as methanol, ethanol, 1-propanol, 1-butanol,
2-methyl-1-propanol, 1-hexanol, 1-octanol, 1-decanol,
1-hexadecanol, 2-buten-1-ol, ethylene glycol, trimethylene glycol,
glycerol, hexamethylene glycol, and pentaerythritol, of which those
having about one to twenty carbon atoms are preferred, those having
about one to fifteen carbon atoms are more preferred, and those
having about one to about six carbon atoms are further preferred;
and primary alcohols having an alicyclic hydrocarbon group (e.g., a
cycloalkyl group) bonded to the carbon atom to which a hydroxyl
group is bonded, such as cyclopropylmethyl alcohol and
2-cyclopropylethyl alcohol.
[0111] Exemplary secondary alcohols include saturated or
unsaturated aliphatic secondary alcohols having about three to
thirty carbon atoms, such as 2-propanol, s-butyl alcohol,
2-pentanol, 3-pentanol, 3,3-dimethyl-2-butanol, 2-octanol,
4-decanol, 2-hexadecanol, 2-penten-4-ol, and vicinal diols such as
glycerol, 1,2-propanediol, 2,3-butanediol, and 2,3-pentanediol, of
which those having about three to twenty carbon atoms are
preferred, those having about three to fifteen carbon atoms are
more preferred, and those having about three to six carbon atoms
are further preferred; secondary alcohols having an aliphatic
hydrocarbon group and an alicyclic hydrocarbon group (e.g., a
cycloalkyl group) bonded to the carbon atom to which a hydroxyl
group is bonded, such as 1-cyclopentylethanol and
1-cyclohexylethanol; and saturated or unsaturated alicyclic
secondary alcohols (inclusive of bridged secondary alcohols) having
about three to twenty members, such as cyclobutanol, cyclopentanol,
and cyclohexanol, of which those having about three to fifteen
members are preferred, and those having about three to six members
are more preferred.
[0112] Exemplary tertiary alcohols include saturated or unsaturated
aliphatic tertiary alcohols having about four to thirty carbon
atoms, such as t-butyl alcohol and t-amyl alcohol, of which those
having about four to twenty carbon atoms are preferred, those
having about four to fifteen carbon atoms are more preferred, and
those having about four to six carbon atoms are further preferred;
tertiary alcohols having an aliphatic hydrocarbon group and an
alicyclic hydrocarbon group (e.g., a cycloalkyl group or a bridged
hydrocarbon group) bonded to the carbon atom to which hydroxyl
group is bonded, such as 1-cyclohexyl-1-methylethanol; and tertiary
alcohols having a hydroxyl group and an aliphatic hydrocarbon group
bonded to one carbon atom constituting an alicyclic ring (e.g.,
cycloalkane ring or a bridged carbon ring), such as
1-methyl-1-cyclohexanol.
[0113] Among these alcohols, methanol, ethanol, propanol,
2-propanol, and butanol are preferably used. The amount of alcohols
is, for example, about 0.1 to 1000 moles, and preferably about 1 to
100 moles, to 1 mole of silicon atoms in the
ethynylphenylbiadamantane derivative of Formula (3a).
[0114] The deprotecting reaction of silyl group is carried out in
the presence of, or in the absence of, an inert solvent. Exemplary
solvents include water; hydrocarbons such as hexane, heptane, and
cyclohexane; aromatic hydrocarbons such as benzene, toluene,
xylenes, and mesitylene; halogenated hydrocarbons such as methylene
chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride;
chain or cyclic ethers such as diethyl ether, dimethoxyethane,
tetrahydrofuran, dioxolane, and diglyme; nitriles such as
acetonitrile and benzonitrile; esters such as ethyl acetate and
butyl acetate; amides such as N,N-dimethylformamide,
N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; ketones such as
acetone, methyl ethyl ketone, and cyclohexanone; and nitro
compounds such as nitromethane and nitrobenzene. Each of these
solvents can be used alone or in combination.
[0115] The reaction temperature is, for example, about -20.degree.
C. to 200.degree. C., preferably about -10.degree. C. to
150.degree. C., and more preferably about 0.degree. C. to
100.degree. C.
[0116] The reaction may be conducted under normal atmospheric
pressure, under reduced pressure, or under a pressure (under a
load). The reaction atmosphere is not particularly limited, as long
as it does not adversely affect the reaction, and can be any of,
for example, air atmosphere, nitrogen atmosphere, and argon
atmosphere. The reaction may be conducted according to any system
such as a batch system, semi-batch system, or continuous
system.
[0117] The reaction product may be separated and purified by a
procedure such as concentration, crystallization, filtration,
washing, recrystallization, precipitation, reprecipitation,
extraction, or column chromatography, or any combination of these
procedures. Typically, the catalyst, salt, and other unnecessary
components may be separated after the completion of reaction by
filtration or by adding water and an organic solvent separable from
water (e.g., toluene or ethyl acetate) to the reaction mixture and
conducing solution washing. When the reaction mixture contains
large amounts of by-products, the reaction product may be separated
and purified using a common separation and purification procedure
such as crystallization, recrystallization, and/or column
chromatography.
[0118] The crystallization is carried out by dissolving the
reaction mixture in a suitable solvent where necessary with
heating, concentrating the solution according to necessity, and
cooling the solution to precipitate crystals. Exemplary solvents
include ethers such as tetrahydrofuran; ketones such as acetone;
hydrocarbons such as toluene; halogenated hydrocarbons such as
chloroform; alcohols such as ethanol; and mixtures of these
solvents. The crystallization is conducted, for example, by using a
combination of a good solvent (e.g., tetrahydrofuran) and a poor
solvent (e.g., methanol) or by using a combination of water and a
water-miscible organic solvent (e.g., tetrahydrofuran, 1,4-dioxane,
acetone, methanol, ethanol, butanol, or acetonitrile).
[0119] Ethynylphenylbiadamantane derivatives according to
embodiments of the present invention excel in solubility in
solvents and have satisfactory properties such as thermal
stability, water resistance, optical properties, optical
transparency, low dielectric constant, and stiffness, and are
thereby usable as starting materials to give functional materials
that excel typically in electrical properties, thermal properties,
mechanical properties, optical properties, and/or physical
properties.
EXAMPLES
[0120] The present invention will be illustrated in further detail
with reference to several examples below. It should be noted,
however, these are illustrated only by way of example and are never
construed to limit the scope of the present invention.
Example 1
[0121] In a 1-liter four-necked flask in a nitrogen atmosphere were
placed 11 g (0.04 mol) of aluminum bromide and 852 g (3.61 mol) of
1,3-dibromobenzene, and the mixture was cooled with stirring to
5.degree. C. The mixture was combined with 50 g (0.1 mol) of
3,3'-dibromo-5,5',7,7'-tetramethyl-1,1'-biadamantane, followed by
stirring at 5.degree. C. for 3 hours and sequentially stirring at
20.degree. C. for 8 hours. After the completion of reaction, 50 g
of 5 N hydrochloric acid and 200 g of water were gradually added to
the reaction mixture while cooling to 10.degree. C. The mixture was
further combined with 250 g of chloroform, followed by separation.
The lower layer was washed with two portions of 300 g of water,
separated, and the precipitates were removed by filtration. The
filtrate was combined with 700 g of toluene, heated to 50.degree.
C., and stirred for 30 minutes. The mixture was cooled to room
temperature to give precipitates, and the precipitates were
collected by filtration, washed with toluene and methanol, dried at
80.degree. C. under reduced pressure, and thereby yielded 73.8 g
(in a yield of 90%) of
3,3'-bis(3,5-dibromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane
represented by following Formula (6):
##STR00016##
[0122] .sup.1H-NMR (CDCl.sub.3, 500 MHz) .delta.: 0.85 (s, 12H),
1.05 (s, 4H), 1.17 (s, 8H), 1.29-1.46 (d, 12H), 7.33 (s, 4H), 7.41
(s, 4H)
[0123] DI/MS-spectrometry: 794, 559, 397 m/z [electron ionization
(EI) detection]
Example 2
[0124] In a 1-liter four-necked flask in a nitrogen atmosphere were
placed 0.34 g of iron (III) chloride, 80 g of benzene, and 10 g of
3,3'-dibromo-5,5',7,7'-tetramethyl-1,1'-biadamantane, and the
mixture was heated to 70.degree. C., followed by stirring for 3
hours. The reaction mixture after the reaction was cooled to
40.degree. C., combined with 30 g of water, stirred for 1 hour, and
separated. The upper layer was concentrated and combined with 20 g
of acetone, followed by stirring at 20.degree. C. for 1 hour. The
precipitated crystals were collected by filtration, and washed with
acetone. Drying at 50.degree. C. under reduced pressure gave 14.2 g
(in a yield of 97%) of
3,3'-di(phenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane.
[0125] .sup.1H-NMR (CDCl.sub.3, 500 MHz) .delta.: 0.83 (s, 12H),
1.02 (q, 4H), 1.19 (q, 8H), 1.34-1.47 (m, 12H), 7.11 (t, 2H), 7.24
(t, 4H), 7.29 (d, 4H)
[0126] GC/MS spectrometry: 478 m/z [electron ionization (EI)
detection]
[0127] In a 1-liter four-necked flask in a nitrogen atmosphere were
placed 9 g of the above-prepared
3,3'-di(phenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane, 0.6 g of
pyridine, 63 g of chloroform, and 7.4 g of bromine, and the mixture
was stirred at 30.degree. C. to 40.degree. C. for 18 hours. The
reaction mixture after the reaction was cooled to 5.degree. C., and
combined with an aqueous sodium sulfite solution to remove excess
of bromine. The mixture was separated, and precipitates in the
lower layer were removed by filtration. The filtrate was combined
with chloroform, water, and sodium hydrogen carbonate, stirred for
1 hour, and separated. The lower layer was washed with water two
times. After washing, the mixture was separated, and the lower
layer was concentrated, combined with methanol, and stirred for 1
hour, followed by crystallization. The precipitated crystals were
collected by filtration, dried at 50.degree. C. under reduced
pressure, and thereby yielded 10.5 g (10.5 mmol; in a yield of 56%)
of 3,3'-bis(4-bromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane
represented by following Formula (7):
##STR00017##
[0128] .sup.1H-NMR (CDCl.sub.3, 500 MHz) .delta.: 0.89 (s, 12H),
1.12 (q, 4H), 1.23 (q, 8H), 1.39-1.48 (m, 12H), 7.22 (d, 2H), 7.41
(d, 4H)
[0129] GC/MS spectrometry: 636 m/z [electron ionization (EI)
detection]
Example 3
[0130] In a 1-liter four-necked flask in a nitrogen atmosphere were
placed 7.34 g (0.044 mol) of iron (III) chloride, 1732 g of
benzene, and 260 g (0.0444 mol) of
3,3',5,5'-tetrabromo-1,1'-biadamantane, and the mixture was heated
to 70.degree. C., followed by stirring for 4 hours. The reaction
mixture after the reaction was cooled to 20.degree. C., combined
with 1040 g of water, stirred for 1 hour, and separated. In
addition, the mixture was washed with two portions of 1040 g of
water, followed by separation. The upper layer was combined with
520 g of methanol and stirred at 5.degree. C. for 1 hour. The
precipitated crystals were collected by filtration and washed with
methanol. Drying at 80.degree. C. under reduced pressure gave 178.5
g (0.13 mol; in a yield of 70%) of
3,3',5,5'-tetraphenyl-1,1'-biadamantane.
[0131] .sup.1H-NMR (CDCl.sub.3, 500 MHz) .delta.: 1.73-1.95 (m,
22H), 2.05 (d, 2H), 2.42 (s, 2H), 7.18 (t, 4H), 7.33 (t, 8H), 7.42
(d, 8H)
[0132] In a 1-liter four-necked flask in a nitrogen atmosphere were
placed 100 g (0.174 mol) of the above-prepared
3,3',5,5'-tetraphenyl-1,1'-biadamantane, 5.64 g (0.035 mol) of iron
(III) chloride, and 1000 g of chloroform, and the mixture was
stirred at 20.degree. C. for 0.5 hour. Next, the mixture was
combined with 124.8 g (0.765 mol) of bromine gradually added,
followed by stirring at 40.degree. C. for 4 hours. The mixture was
further combined with 128.4 g (0.765 mol) of bromine gradually
added, followed by stirring at 40.degree. C. for 6 hours. The
reaction mixture after the reaction was cooled to 5.degree. C., and
combined with an aqueous sodium sulfite solution to remove excess
of bromine. Next, the mixture was separated, and precipitates were
removed by filtration. The filtrate was concentrated, combined with
hexane, and stirred at 20.degree. C. for 1 hour, followed by
crystallization. The precipitated crystals were collected by
filtration and washed with hexane. Drying of the obtained crystals
at 60.degree. C. under reduced pressure gave 108 g (0.121 mol; in a
yield of 70%) of
3,3',5,5'-tetrakis(4-bromophenyl)-1,1'-biadamantane represented by
following Formula (8):
##STR00018##
[0133] .sup.1H-NMR (CDCl.sub.3, 500 MHz) .delta.: 1.70-2.03 (m,
24H), 2.45 (s, 2H), 7.26 (d, 8H), 7.43 (d, 8H)
[0134] FAB-MS-spectrometry: 890 m/z
Example 4
[0135] In a 1-liter four-necked flask in a nitrogen atmosphere were
placed 212.7 g (0.264 mol) of
3,3'-bis(3,5-dibromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane,
14.8 g (0.021 mol) of dichlorobis(triphenylphosphine)palladium,
27.74 g (0.106 mol) of triphenylphosphine, 20.14 g (0.106 mol) of
copper iodide, 1470 g of triethylamine, and 630 g of toluene, and
the mixture was heated to 70.degree. C. and stirred. After the
temperature rise, 77.9 g (0.793 mol) of trimethylsilylacetylene was
gradually added over 1 hour, followed by stirring at 70.degree. C.
for 1 hour. In addition, 52 g (0.529 mol) of
trimethylsilylacetylene was gradually added over 1 hour, followed
by stirring at 70.degree. C. for 7 hours. The reaction mixture
after the reaction was concentrated, combined with 2000 g of
toluene, stirred at 30.degree. C. for 1 hour, and insoluble
components were separated therefrom by filtration. The filtrate was
combined with 180 g of 5 N hydrochloric acid and 500 g of water,
the mixture was adjusted to have a pH of 6 and then separated. The
upper layer was washed with water two times, separated,
concentrated, cooled to 20.degree. C., and combined with 800 g of
acetone gradually added, followed by crystallization. The
precipitated crystals were collected by filtration and washed with
acetone. To 205 g of the wet crystals was added 1000 g of toluene,
the mixture was heated to 50.degree. C. to give a solution, and the
solution was cooled to 20.degree. C. Next, 2000 g of acetone was
gradually added, followed by crystallization. The precipitated
crystals were collected by filtration, washed with acetone, dried
at 80.degree. C. under reduced pressure, and thereby yielded 169 g
(0.196 mol; in a yield of 73%) of
3,3'-bis(3,5-trimethylsilylethynylphenyl)-5,5',7,7'-tetramethyl-1,1'-biad-
amantane represented by following Formula (9):
##STR00019##
[0136] .sup.1H-NMR (CDCl.sub.3, 500 MHz) .delta.: 0.25 (s, 36H),
0.91 (s, 12H), 1.07 (s, 4H), 1.20 (s, 8H), 1.35-1.52 (m, 8H), 1.44
(s, 4H), 7.40 (s, 4H), 7.43 (s, 4H)
[0137] GC/MS spectrometry: 862.37 m/z [M+]
Example 5
[0138] In a 1-liter four-necked flask in a nitrogen atmosphere were
placed 10 g (4.6 mmol) of
3,3'-bis(3,5-trimethylsilylethynylphenyl)-5,5',7,7'-tetramethyl-1,1'-biad-
amantane, 0.64 g (4.6 mmol) of potassium carbonate, 100 g of
tetrahydrofuran, and 50 g of methanol, and the mixture was stirred
at 30.degree. C. for 4 hours. The reaction mixture after the
reaction was combined with 50 g of methanol, stirred at 20.degree.
C. for 1 hour, and the precipitated crystals were collected by
filtration. The crystals were dissolved in chloroform with heating,
and the solution was washed with water and separated. The lower
layer was concentrated, combined with methanol, and the
precipitated crystals were collected by filtration and washed with
methanol. Drying of the resulting crystals at 50.degree. C. under
reduced pressure gave 6.3 g (11 mmol; in a yield of 95%) of
3,3'-bis(3,5-ethynylphenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane
represented by following Formula (10):
##STR00020##
[0139] .sup.1H-NMR (CDCl.sub.3, 500 MHz) .delta.: 0.84 (s, 12H),
1.02 (s, 4H), 1.22 (s, 8H), 1.38-1.51 (m, 12H), 3.01 (s, 4H), 7.45
(s, 2H), 7.47 (s, 4H)
Example 6
[0140] In a 1-liter four-necked flask in a nitrogen atmosphere were
placed 1.0 g (1.26 mmol) of
3,3'-bis(3,5-dibromophenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane,
0.071 g (0.1 mmol) of dichlorobis(triphenylphosphine)palladium,
0.132 g (0.5 mmol) of triphenylphosphine, 0.096 g (0.5 mmol) of
copper iodide, 11 g of triethylamine, and 5 g of toluene, and the
mixture was heated to 70.degree. C. and stirred. After the
temperature rise, 1.03 g (10.0 mmol) of phenylacetylene was
gradually added over 1.5 hour, followed by stirring with heating at
70.degree. C. for 12 hours. The reaction mixture after the reaction
was concentrated, combined with 64 g of toluene, stirred at
50.degree. C. for 1 hour, and insoluble components were separated
therefrom by filtration. The filtrate was combined with 10 g of 5 N
hydrochloric acid and separated. The upper layer was washed with
water two times, concentrated, cooled, and the precipitated
crystals were collected by filtration and washed with acetone.
Drying of the obtained wet crystals at 80.degree. C. under reduced
pressure gave 0.72 g (0.82 mmol; in a yield of 65%) of
3,3'-bis(3,5-phenylethynylphenyl)-5,5',7,7'-tetramethyl-1,1'-biadamantane
represented by following Formula (11):
##STR00021##
[0141] DI/MS-spectrometry: 879.25 m/z [electron ionization (EI)
detection]
[0142] Examples 1 to 6 demonstrate that processes according to
embodiments of the present invention yield halophenylbiadamantane
derivatives and ethynylphenylbiadamantane derivatives according to
embodiments of the present invention in high yields.
[0143] While there have been described what are at present
considered to be the preferred embodiments of the present
invention, it should be understood by those skilled in the art that
various modifications, combinations, subcombinations, and
alterations may occur depending on design requirements and other
factors insofar as they are within the spirit and scope of the
appended claims or the equivalents thereof.
* * * * *